Process for breaking petroleum emulsions



Patented Nov. 3, 1942 PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin DeGroote, University City, and Bernhard Keiser, Webster Groves, Mo.,assignors to Petrolite Corporation, Ltd., Wilmington, Dei., acorporation of Delaware No Drawing. Application May 12, 1941, Serial No.393,130

4 Claims. (Cl. 252-334) 'in a more or less permanent state throughoutthe oil which constitutes the continuous phase of the emulsion.

"Another object of our invention is to provide aneconomical and rapidprocess for separating emulsions which have been prepared undercontrolled conditions from mineral oil, such as crude oil and relativelysoft waters or weak brines. Controlled emulsiflcation and subsequentdemulsification under the conditions just mentioned is of significantvalue in removing impuritiies, particularly inorganic salts from pipeline l.

The process, which constitutes our present invention, consists insubjecting a petroleum emulsion of the water-in-oil type to the actionof a' demulsifier or demulsifying agent, thereby causing the emulsion tobreak and separate into its component parts of oil and water or brine,when the emulsion is permitted to remain in a quiescent state aftertreatment, or is subjected to other equivalent separatory procedure. Thedemulsifying agent employed in our process comprises a chemical compoundconsisting of the.

salt of a basic amine. The amine salts intended to be used as thedemulsifier of our process are of the kind exemplified by salts derivedfrom diacetone amine, triacetone amine, etc. They are derivatives of thewater-soluble type of petroleum sulfonic acid, commonly known as greenacids. Petroleum sulfonic acids are produced from a wide variety ofpetroleum distillates or petroleum fractions, and in some instancesthey.

are produced from the crude petroleum itself. when produced from crudepetroleum itself it is customary to use crude oil of the naphthenictype, crude oil of the paraflin type, crude oil of the asphaltic typeand mixtures of said three diil'erent types of crude oil.

The art of refining crude petroleum or various fractions, using sulfuricacid of various strengths, as well as monohydrate and fuming acid, is awell known procedure. In such conventional refining procedure, petroleumsulfonic acids have mahogany acids also show limited ydrophilic beenproduced as by-products. For instance. in

removing the olefinic components, it has been common practice to usesulfuric acid so as to polymerize the olefines or convert them intosulfonic acids which are subsequently removed. Likewise, in theproduction of white oil, or highly refined lubricating oils, it has beencustomary to treat with fuming sulfuric acid, so as to eliminate certainundesirable components.

In recent years, certain mineral oil fractions have been treated withsulfuric acid with the primary object of producing petroleum sulfonicacids, and in such procedure the petroleum sulfonic acids representedthe primary products of reaction rather than concomitant by-products.

Petroleum sulfonic acid, regardless of whether derived as the principalproduct of reaction or as a by-product, can be divided into two generalproducts, to wit, green acid or acids and mahogany acid or acids. Thegreen acids are characterized by being water-soluble or dispersible. Inother words, they form either true solutions or sols. For purpose ofconvenience, they will be herein referred to as water-soluble, withoutany effort to indicate whether the solution is molecular or colloidal innature. The green acids, as indicated by their name, frequently give anaqueous solution having a dark green or greyappearance. They generallyappear as a component of the acid draw-oft, and do not remain behinddissolved in the oil fraction which has been subjected to sulfuric acidtreatment. The green acids are not soluble in oil, even whensubstantially anhydrous, and certainly are not soluble in oil when theycontain as much as I5% of water. Similarly, their salts obtained byneutralizing the green acids with a strong solution of caustic soda,caustic potash, or ammonia, are not oil-soluble. For convenience ofclassification. the ammonium salt will be considered as an alkali salt.

In contradistinction to the hydrophile green acids, there occurs as inthe manufacture of medicinal white oil, the oil-soluble type or themahogany acids. These mahogany acids are characterized by being solublein oil, especially when anhydrous, and being soluble in oil, even ifthey contain some dissolved water. Some of the properties to the extentthat either some water can be dissolved in the acids, or they, in turn,may dissolve to some extent in water. In some instances their salts.such as the sodium, ammonium, or potassium salt, will dissolve in waterto give a colloidal sol. However, regardless of the presence of anyhydrophilic properties whatketone, methyl normal amyl ketone, etc. Thus,referring to the previous formula'for triacetone amine, it is obviousthat instead of an amine having nine carbon atoms, one may obtaincomparable ketone amines in which amyl groups, for example, appear atleast twice, as a. substituent for a hydrogen atom of a methyl group,with the re- The utility of the mahogany acids in various arts has beenenhanced by increasing their wa-- ter-solubility; for instance,converting the mahogany acids into hydroxy alkylamine salts. 0n theother hand, as far as we are aware, no valuable product of commerce hasresulted from decreasing the water solubility of the mahogany acids bythe addition of some oil-soluble basic amine, such as, for example,triamylamine. The triamylaminesalts of mahogany acids, for example, arecompletely devoid of any solubility in water which the alkalisalts mayhave exhibited and show, as would be expected, an increased solubilityin hydrophobe solvents.

Green acids are hydrophile in character, as previously stated. Theirhydrophile character has been increased by neutralization with materialssuch as triethanolamine and the like. Such green acid salts, havingenhanced water solubility, as compared with the ordinary alkali salts,have found application in certain arts.

We have found that if green acids, i. e., the

' oil-insoluble type, are neutralized with a ketone amine of the kindhereinafter described, the resulting product has pronounced value as ademulsifler for oil field emulsions of the water-inoil type, either whenused alone, or when used in coniunuction with other compatibleand wellknown demulsifying agents. The ketone amines, particularly acetoneamines, most suitable for neutralizing the green acids to give compoundsof the kind herein contemplated, are best illustrated by 'diacetoneamine and triacetone amine. The structural formula for diacetone amineis as follows:

(cubic-ornament) Similarly, the formula for triacetone amine is asfollows:

NH 0 t (CH3): 'CH:

These compounds are obtained by the action of ammonia on mesityl oxideand phorone. The structural formula for mesityl oxide is asfollows:

CHa

- cm I The structural formula for phorone is as follows:

Insofar that the reactions leading to the formation of mesityl oxide andphorone are dependent primarily on the presence of an alphahydrogenatom, it becomes obvious that either by direct or indirect methods onecan obtain alkylzted or substituted ketone amines which may beconsidered as derivatives of other available keton-ra, such as, forexample, methyl isobutyl sult that such amines may contain as many asseventeen carbon atoms. Similarly, other ketone amines illustrate avariation in carbon atom content from nine to seventeen carbon atoms.

The manufacture of the demulsifier employed in our process contemplatesnothing more nor less than neutralizing the selected petroleum sulfonicacid with a suitable amineuntil neutral to litmus. indicator, or to someother suitable indicator. For purposes of convenience we prefer that theselected petroleum sulfonic acid contain'not over 15% of water. It is,of course, understood that the conventional procedure employing doubledecomposition instead of direct neutralization can be employed in themanufacture of our new material or composition of matter.

'We are aware that at least in a number of instances, comparable aminesare obtainable by the use of an amine other than a tertiary amine toreplace ammonia as a reactant iii-combination with mesityl oxide,phorone, etc. In such compounds the amlno nitrogen atom or atoms of theketone amines above described, are replaced by suitable hydrocarbonradicals, such as alkyl radicals, aralkyl radicals, alicyclic radicals,etc.. as for example, when amylamine; cyclohexylamine, benzylamine, etc.replace ammonia as a reactant.

In order to designate the amines of the kind herein contemplated asreactants, they will be referred to as the class consisting of diacetoneamine, triacetone amine, carbonatom linked alkylated diacetone aminescontaining not over seventeen carbon atoms, and carbon atom linkedalkylated triacetone amines containing not over seventeen carbon atoms.vReferencetothefactthat the alkylation is carbon atom linked is intendedto eliminate from present consideration alkylated derivatives of'diacetone amine, triacetone amine, and the like, in which the alkylgroup or groups substituted in the compound or compounds replace anamino hydrogen atom, and thus are nitrogen linked.

It may bewell to point out that hydrophile non-hydrophobe petroleumsulfonic acid or acids of the green acid type vary somewhat; forinstance, the molecular weightmay vary within the range of 350-500, orthereabouts. Natural- 13, these petroleum sulfonic acids may carry somepolymerized olefines, free hydrocarbons, or the like, or may even carrya bit of naphthenic acids which represent carboxylated non-sulfonatedpetroleum acids. As previously stated, these materials are well-knowncommercial products and areavailable in the open market, either in theform of the acid itself, or in the form of a salt.

The amines 'above described may properly be referred to as-basic,inasmuch as the basicity is in the neighborhood of that of ammonia. Thisis obvious, insofar that no amino hydrogen atom has been replaced by anaryl group, an acyl moisture content is not over 15%.

enteen carbon atoms. Whether-or-not a-waterinsoluble salt is produced,depends, in part, on the molecular weight, and as has been previouslyindicated, this property may show some variation.

'Althoughjit .is believed, in view or what has been said previously,that no furtherdscription is required in regard to themanufacturep! the,Greenacids are obtained-from lubricating, cii distillate having an s.U. viscosit Hat 150 F. of about 400 seconds. The procedure employed inobtaining such green, acids is that described in U. S. Patent No.2,188,770, dated January 30,1940, to Robertson. The material so obtained'contains'iconsiderable moisture and is preferably dehydrated to' thepoint where the Thesulfonic acid isthen neutralizedtoI-litmus indicatorwith diacetone amine.

Example 2 The same procedure is followed as in Example 1, but instead,the green acids are obtained from Gulf Coast transformer oil extract inthe manner described in U. S. Patent No. 2,203,443, dated June 4, 1940,to Ross and Mitchell.

Example 3 The same procedure is followed asin Example 2, except thatCalifornia 65 Baybolt viscosity Edeleanu extract is employed instead ofGulf Coast transformer Edeleanu extract employed in Example 2.

Example 4 The same procedure is followed as in Example 1, except thatthe product is made from aGuli' Coast naphthene type crude, preferablyof the kind which has little or no low boiling fraction, 1. e., the kindwhich, on a straight run distillation, gives little or no gasoline.

Example 5 The same procedure is followed as in Examples 1-4, inclusive,except that triacetone amine is employed instead of diacetone amine.

Example 6 alcohol, denaturedalcohol, propyl alcohol, butyl alcohol,hexyl alcohol, ocetyl alcohol, etc., may be employed as diluents.Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfurdioxide extract obtained in the refining of petro leum, etc., may beemployed as diluents. Similarly. the material or materials employed asthe demulsifying agent oi our process may be admixed wlth one or more ofthe solvents customarily used in connection with conventionalmaterialsmay be used alone, or in admixture with other suitable wellknown classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in awater-soluble form, or in anoil -"solubleform, or in a form exhibitingboth oil and-water solubility. Sometimes they may be used in a formwhich exhibits relatively limited oil solubility. However, since suchreagents are sometimesused in a ratio of 1 to 10,000, or 1 to 20,000, oreven 1 to 30,000, such an apparent insolubility in oil and water isnotsignificant, becausesaid reagents undoubtedly have solubility within theconcentration employed. This same fact is true in regard to the materialor materials employed as the demulsifying agent of our We desire topoint out that the superiority of the reagent or demulsifying agentcontemplated in our process is based upon its ability to treat certainemulsions more advantageously and at a somewhat lower cost than ispossible with other available-demulsifiers, or conventional mixturesthereof. It is believed that the particular demulsifying agent ortreating agent herein described will find comparatively limitedapplication, so far as the majority of oil field emulsions areconcerned: butwe have found that such a demulsifying agent hascommercial value, as it will economically break or resolve oil fieldemulsions in. a number of cases which cannot be treated as easily or atso low a cost with the demulsifying agents heretofore available.

In practising our process, a treating agent or demulsifying agent of thekind above described is brought into contact with or caused to act uponthe emulsion to be treated, in any of the various ways, or by any'of thevarious apparatus now generally used. to resolve or break petroleumemulsions with a chemical reagent, the above procedure being used eitheralone or in combinationwith other demulsifying procedure, such as theelectrical dehydration process.

The demulsifi'er herein contemplated may be employed in connection withwhat is commonly known as down-the-hole procedure, i. e., bringing thedemulsifler in contact with the fluids of the well at the bottom of thewell, or at some point prior to their emergence. This particular type ofapplication is decidedly feasible when the demulsifier is used inconnection with acidification of calcareous oil-bearing strata,especially if suspended in or dissolved in the acid employed foracidification.

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent is:

1..A process for resolving petroleum emulsions of the water-in-oil type,characterized bysubiecting the emulsion to the action of a demulsifiercomprising a chemical compound, consisting of the salt of a basic amine;said amine salt bein obtained. from a water-soluble, non-hydrophobepetroleum sulfonic acid of the green acid type, and a ketone amineselected from the class consisting of diacetone amine, triacetone amine,carbon atom linked alkylated diacetone amines containing not over 17carbon atoms, and carbon atom linked alkylated triacetone aminescontaining not over 1'7 carbon atoms.

2. A process for resolving petroleum emulsions of the water-in-oiltype,characterized by subjectinr the emulsion to the action of a demulsiflercomprising-a chemical compound, consisting of demulsifying agents.Moreover, said material or the salt of a basic amine; said amine saltbeing obtained from a water-soluble, non-hydrophobe petroleum sulionicacid of the green acid type. and a ketone amine selected from. the classcon sisting of diacetone amine, triacetone amine, carbon atom linkedalkylateddiacetone amines containing not over 17 carbon atoms, andcarbon atom linked aliq'lated triacetone amines containing not over 17carbon atoms; said green acid being obtained from a naphthene typecrude.

3. A process for resolving petroleum emulsions of the water-in-oil type,characterized by subject ing the emulsion to the action of a demulsiflercomprising a chemical compound, consisting of the salt of a basic amine;saiol amine salt bein obtained from a water-soluble, non-hydrophobepetroleum sulfonic acid of the greeen acid type, and a ketone M 1 50,selected from the class consisting of diacetcne amine, triacetone amine,car= bon atom linked allzylated diacetone amines conthe salt of a basicamine; said amine salt bein taming not over liicarbon atoms, and carbon2o obtained from a water-soluble, non-hydrophobe petroleum. sulfonicacid of the green acid type, and a ketone amine selected from the classconsisting of diacetone amine, triacetone amine, carbon atom linkedalkylated diaOetone amines containing not over 17 carbon atoms, andcarbon atom linked allsylated triacetone amines containing not over 17carbon atoms; said green acid being obtained from an asphaltic crude.

MJELWIN DE GROOTE. IBERD KEISER.

